EP0690836B1 - Verfahren zur isomerisierung von carbonsäuren - Google Patents

Verfahren zur isomerisierung von carbonsäuren Download PDF

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Publication number
EP0690836B1
EP0690836B1 EP94909156A EP94909156A EP0690836B1 EP 0690836 B1 EP0690836 B1 EP 0690836B1 EP 94909156 A EP94909156 A EP 94909156A EP 94909156 A EP94909156 A EP 94909156A EP 0690836 B1 EP0690836 B1 EP 0690836B1
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EP
European Patent Office
Prior art keywords
process according
acid
reaction
acids
carried out
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Expired - Lifetime
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EP94909156A
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English (en)
French (fr)
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EP0690836A1 (de
Inventor
Philippe Denis
Carl Patois
Robert Perron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Fiber and Resin Intermediates SAS
Original Assignee
Rhone Poulenc Fibres SA
Rhodia Fiber and Resin Intermediates SAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton

Definitions

  • the present invention relates to a process for the isomerization of acids carboxylic acids, more specifically branched saturated carboxylic acids, into acids corresponding lines.
  • the present invention is characterized by the use of iridium, a catalyst different from that previously described for this reaction.
  • it consists of an isomerization process by heating, at least one branched saturated carboxylic acid, characterized in that operates in the presence of an effective amount of an iridium catalyst and a promoter iodinated or brominated, the promoter / lr molar ratio being between 0.1 / 1 and 20/1.
  • the branched diacids are from an economic point of view the most interesting to value, due to the strong quantities formed during the hydroxycarbonylation of pentenoic acids for the preparation of adipic acid.
  • 2-methyl-glutaric acid 2-ethyl-succinic acid and their mixtures with each other and / or with other carboxylic acids or lactones formed at the same time as them, such as adipic acid, pentenoic acids, valeric acid, gamma-valerolactone.
  • the compounds other than 2-methylglutaric acid and 2-ethyl-succinic acid can represent up to 50% by weight of the total weight of the mixture.
  • iridium catalyst For the iridium catalyst required in the present process, various sources of iridium are likely to be used.
  • the iridium catalysts which are more particularly suitable are: [lrcl (cod)] 2 , lr 4 (CO) 12 and lr (acac) (CO) 2 .
  • the amount of catalyst to be used can vary within wide limits. limits.
  • an amount, expressed in moles of iridium metal per liter of reaction mixture, of between 10 -4 and 10 -1 leads to satisfactory results. Smaller amounts can be used, but it is observed however that the reaction rate is low. Larger quantities have disadvantages only economically.
  • the concentration of iridium in the reaction mixture is between 5.10 -4 and 5.10 -2 mole / liter.
  • iodinated or brominated promoter in the context of the process iodide of hydrogen, hydrogen bromide and organo-iodine and organo-bromine compounds capable of generating hydrogen iodide and hydrogen bromide respectively under the reaction conditions; these organo-iodinated and organo-brominated compounds are more particularly iodides and alkyl bromides having from 1 to 10 atoms of carbon, of which methyl iodide and methyl bromide are preferred.
  • the promoter / lr molar ratio is preferably between 1/1 and 10/1.
  • the reaction is carried out in the liquid phase.
  • the temperature at which generally operates from 120 ° C to 300 ° C and preferably from 150 ° C to 250 ° C.
  • isomerization can be carried out according to the process of the invention in the absence of carbon monoxide, it is preferable to operate in its presence.
  • the total pressure at the reaction temperature can then vary within wide limits.
  • the partial pressure of carbon monoxide, measured at 25 ° C, is generally from 0.5 bar to 100 bars and preferably from 1 bar to 80 bars.
  • the carbon monoxide used can be carbon monoxide substantially pure or technical grade carbon monoxide, as found in the trade.
  • the isomerization reaction of branched saturated carboxylic acids is conducted either in the acid itself as the liquid medium of the reaction, or in a third solvent.
  • carboxylic acids aliphatic, saturated or unsaturated, or aromatic, containing at most 20 atoms of carbon, insofar as they are liquid under the reaction conditions.
  • carboxylic acids include acetic acid, acid propionic, butanoic acid, valeric acid, adipic acid, acids pentenoics, benzoic acid and phenylacetic acid.
  • solvents can also be used, in particular saturated aliphatic or cycloaliphatic hydrocarbons and their chlorinated derivatives, insofar as they are liquid under the reaction conditions.
  • the solvent represents example from 10% to 99% by volume relative to the total volume of said mixture reaction and preferably from 30% to 90% by volume.
  • Water is most often present in the reaction mixture. Generally, it represents from 0 to 20% by weight of the reaction mixture and preferably 0-10%.
  • a interesting variant consists in operating in a water / water-miscible solvent mixture, such as for example water / acetic acid.
  • a water / water-miscible solvent mixture such as for example water / acetic acid.
  • the values of proportions of the water / water-miscible solvent mixture in the reaction mixture are those which have been indicated previously for the sole solvent.
  • the isomerization process according to the invention makes it possible to develop in particular the branched saturated dicarboxylic acids obtained in more or less quantities important during the hydroxycarbonylation of pentenoic acids. This allows a increase in the overall yield of a process for the preparation of adipic acid from butadiene via pentenoic acids, adipic acid being one of the materials raw materials for the preparation of polyamides 6-6.
  • the final reaction mixture is treated according to conventional methods used in chemistry, in order to separate the different compounds formed and the saturated acids branched plants which have not reacted, the latter may be subject to a new isomerization.
  • the process according to the invention can be carried out continuously or in discontinuous.
  • the relative ratios of reactants, catalyst, promoter and solvent can be set to an optimal value by a person skilled in the art, whereas generally in a process implemented batchwise, these different reports evolve according to the progressive transformation of the reagents.
  • the autoclave is closed, placed in a stirred oven and connected to the power supply CO under pressure. 5 bar of CO is put at 25 ° C, then heated to 230 ° C. We adjust the pressure at temperature at 25 bar using CO (which corresponds to 17 bar of partial pressure of CO measured at 25 ° C) and this pressure is maintained for 5 hours at 230 ° C.
  • the autoclave is then cooled, then degassed and the reaction mixture is analyzed by gas chromatography (GC) and liquid chromatography at high performance (HPLC).
  • GC gas chromatography
  • HPLC high performance
  • Example 1 is repeated, under the same conditions and with the same amounts of the same reagents, but using 2.5 mmol of hydrogen iodide and 0.42 mmol of [lrCl (cod)] 2 .
  • Example 1 is repeated, under the same conditions and with the same amounts of the same reagents, but using 2.5 mmol of hydrogen iodide and operating at 200 ° C.
  • Example 3 is repeated, under the same conditions and with the same quantities of the same reagents, but without connecting the autoclave to the supply of carbon monoxide.
  • the glass bulb is placed in a 125 cm 3 autoclave, previously purged with argon.
  • the autoclave is closed, placed in a stirred oven and connected to the pressurized CO supply.
  • 5 bar of CO is put at 25 ° C, then heated to 230 ° C.
  • the temperature pressure is adjusted to 100 bar using CO (which corresponds to 59 bar of partial CO pressure measured at 25 ° C) and this pressure is maintained for 2 hours at 230 ° C.
  • the autoclave is then cooled, then degassed and the reaction mixture is analyzed by CPG and HPLC.
  • Example 5 is repeated, under the same conditions and with the same quantities of the same reagents, but operating under a CO pressure of 25 bar at 230 ° C instead of 100 bar.
  • Example 5 is repeated, under the same conditions and with the same quantities of the same reagents, but operating under a CO pressure of 25 bar at 230 ° C instead of 100 bar and leaving to react for 30 min at temperature instead of 2 hrs.
  • Example 5 is repeated, under the same conditions and with the same quantities of the same reagents, but operating under a CO pressure of 10 bar at 230 ° C instead of 100 bar.
  • Example 5 is repeated, under the same conditions and with the same quantities of the same reagents, but operating at a temperature of 200 ° C instead of 230 ° C.
  • Example 6 is repeated, under the same conditions and with the same quantities of the same reagents, but operating at a temperature of 200 ° C instead of 230 ° C.
  • Example 8 is repeated, under the same conditions and with the same quantities of the same reagents, but operating at a temperature of 200 ° C instead of 230 ° C.
  • Example 6 is repeated, under the same conditions and with the same amounts of the same reagents, but additionally loading 7.25 mmol of water initially.
  • Example 5 is repeated, under the same conditions and with the same amounts of the same reagents, but replacing HI with 0.54 mmol of 47% HBr in weight in water.
  • Example 6 is repeated, under the same conditions and with the same amounts of the same reagents, but replacing HI with 0.54 mmol of 47% HBr in weight in water.
  • Example 8 is repeated, under the same conditions and with the same amounts of the same reagents, but replacing HI with 0.54 mmol of 47% HBr in weight in water.
  • Example 5 The procedure is as in Example 5, with a CO pressure in temperature of 25 bars and maintaining the test at 230 ° C for 5 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (14)

  1. Verfahren zur Isomerisierung durch Erhitzen von zumindest einer gesättigten verzweigten Carbonsäure, dadurch gekennzeichnet, daß man in Gegenwart einer wirksamen Menge eines Iridiumkatalysators und eines brom- oder jodhaltigen Promotors arbeitet, wobei das Molverhältnis Promotor/Ir zwischen 0,1:1 und 20:1 liegt.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß die eingesetzte gesättigte verzweigte Carbonsäure unter 2-Methylglutarsäure, 2-Ethyl-bernsteinsäure und deren Gemischen untereinander und/oder mit anderen gleichzeitig mit ihnen gebildeten Carbonsäuren oder Lactonen wie Adipinsäure, die Pentensäuren, Valeriansäure und Gamma-Valerolacton ausgewählt wird.
  3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, daß in dem eingesetzten Gemisch die anderen Verbindungen als 2-Methylglutarsäure und 2-Ethyl-bernsteinsäure höchstens 50 Gew.-%, bezogen auf das Gesamtgewicht des Gemisches, ausmachen.
  4. Verfahren gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß der eingesetzte Iridiumkatalysator ausgewählt wird unter:
    Ir metallisch; IrO2; Ir2O3;
    IrCl3 ;lrCl3, 3H2O ;
    IrBr3 ; IrBr3, 3H2O ;
    lrl3 ;
    lr2(CO)4Cl2 ; lr2(CO)4l2 ;
    lr2(CO)8 ; lr4(CO)12 ;
    lr(CO)[P(C6H5)3]2l ;
    Ir(CO)[P(C6H5)3]2Cl ;
    lr[P(C6H5)3]3l ;
    Hlr[P(C6H5)3]3(CO) ;
    lr(acac)(CO)2 ;
    [IrCl(cod)]2 .
  5. Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß die Katalysatormenge, ausgedrückt in Mol Iridiummetall je Liter Reaktionsgemisch, zwischen 10-4 und 10-1, und bevorzugt zwischen 5 x 10-4 und 5 x 10-2 Mol/l beträgt.
  6. Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß der jod- oder bromhaltige Promotor unter Jodwasserstoff, Bromwasserstoff und den jodorganischen und bromorganischen Verbindungen, die imstande sind, Jodwasserstoff bzw. Bromwasserstoff unter den Reaktionsbedingungen zu liefern, ausgewählt wird.
  7. Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß das Molverhältnis Promotor/Ir zwischen 1:1 und 10:1 beträgt.
  8. Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Reaktion in Anwesenheit von Kohlenmonoxid unter einem Kohlenmonoxidpartialdruck, gemessen bei 25°C, von 0,5 bar bis 100 bar und bevorzugt 1 bar bis 80 bar durchgeführt wird.
  9. Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Reaktion in flüssiger Phase bei einer Temperatur von 100 bis 300°C und bevorzugt 150 bis 250°C durchgeführt wird.
  10. Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Isomerisierungsreaktion der Carbonsäure in der Carbonsäure selbst als flüssigem Reaktionsmedium durchgeführt wird.
  11. Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Isomerisierungsreaktion der gesättigten verzweigten Carbonsäure in einem dritten Lösungsmittel, ausgewählt unter Benzol, Toluol, Chlorobenzol, den gesättigten oder ungesättigten aliphatischen oder den aromatischen Carbonsäuren mit höchstens 20 Kohlenstoffatomen, den gesättigten aliphatischen oder cycloaliphatischen Kohlenwasserstoffen und deren chlorierten Derivaten, die unter den Reaktionsbedingungen flüssig sind, durchgeführt wird.
  12. Verfahren gemäß Anspruch 11, dadurch gekennzeichnet, daß das Lösungsmittel 10 bis 99 Vol.%, bezogen auf das Gesamtvolumen des Reaktionsgemisches, und bevorzugt 30 bis 90 Vol.%, ausmacht.
  13. Verfahren gemäß einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Reaktion in Gegenwart von Wasser durchgeführt wird.
  14. Verfahren gemäß einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß das Wasser 0 bis 20 Gew.% des Reaktionsgemisches, und bevorzugt 0 bis 10%, ausmacht.
EP94909156A 1993-03-25 1994-03-07 Verfahren zur isomerisierung von carbonsäuren Expired - Lifetime EP0690836B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9303703A FR2703045B1 (fr) 1993-03-25 1993-03-25 Procédé d'isomérisation d'acides carboxyliques.
FR9303703 1993-03-25
PCT/FR1994/000247 WO1994021586A1 (fr) 1993-03-25 1994-03-07 Procede d'isomerisation d'acides carboxyliques

Publications (2)

Publication Number Publication Date
EP0690836A1 EP0690836A1 (de) 1996-01-10
EP0690836B1 true EP0690836B1 (de) 1998-08-19

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EP94909156A Expired - Lifetime EP0690836B1 (de) 1993-03-25 1994-03-07 Verfahren zur isomerisierung von carbonsäuren

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EP (1) EP0690836B1 (de)
JP (1) JP3091493B2 (de)
KR (1) KR100288999B1 (de)
CN (1) CN1046264C (de)
BR (1) BR9406166A (de)
CA (1) CA2156418A1 (de)
CZ (1) CZ287045B6 (de)
DE (1) DE69412599T2 (de)
FR (1) FR2703045B1 (de)
PL (1) PL174067B1 (de)
RU (1) RU2123490C1 (de)
SG (1) SG74551A1 (de)
SK (1) SK281756B6 (de)
TW (1) TW287155B (de)
UA (1) UA44242C2 (de)
WO (1) WO1994021586A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292944A (en) * 1993-06-29 1994-03-08 E. I. Du Pont De Nemours And Company Process for the preparation of adipic acid or pentenoic acid
FR2749582B1 (fr) * 1996-06-07 1998-07-17 Rhone Poulenc Fibres Procede d'hydroxycarbonylation des acides pentenoiques
EP3887596A4 (de) 2018-11-29 2022-08-24 RISE Innventia AB Verfahren zur herstellung von holocellulose und papierfestigkeitsmittel, verfahren zur herstellung von papier, hergestelltes papier und verwendung des hergestellten papiers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3090807A (en) * 1958-07-31 1963-05-21 Basf Ag Isomerization of saturated aliphatic carboxylic acids
US3578688A (en) * 1968-05-03 1971-05-11 Union Oil Co Isomerization of acids
US3592849A (en) * 1969-01-21 1971-07-13 Union Oil Co Decomposition of anhydrides to isomeric acids
JPS6245854A (ja) * 1985-11-25 1987-02-27 不二サッシ株式会社 太陽エネルギー収集屋根の下部接続部材
US4939298A (en) * 1988-12-12 1990-07-03 E. I. Du Pont De Nemours And Company Isomerization of carboxylic acids

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Publication number Publication date
RU2123490C1 (ru) 1998-12-20
WO1994021586A1 (fr) 1994-09-29
PL174067B1 (pl) 1998-06-30
SK117595A3 (en) 1996-04-03
TW287155B (de) 1996-10-01
JP3091493B2 (ja) 2000-09-25
SK281756B6 (sk) 2001-07-10
JPH08506349A (ja) 1996-07-09
FR2703045A1 (fr) 1994-09-30
CZ244195A3 (en) 1996-01-17
SG74551A1 (en) 2000-08-22
DE69412599D1 (de) 1998-09-24
UA44242C2 (uk) 2002-02-15
CA2156418A1 (fr) 1994-09-29
CZ287045B6 (en) 2000-08-16
CN1046264C (zh) 1999-11-10
EP0690836A1 (de) 1996-01-10
KR960700990A (ko) 1996-02-24
KR100288999B1 (ko) 2001-05-02
CN1119855A (zh) 1996-04-03
FR2703045B1 (fr) 1995-05-19
PL310682A1 (en) 1995-12-27
DE69412599T2 (de) 1999-05-27
BR9406166A (pt) 1996-01-09

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